CN113194922B

CN113194922B - Microemulsion composition, cured product thereof, and cosmetic containing cured product thereof

Info

Publication number: CN113194922B
Application number: CN201980082651.0A
Authority: CN
Inventors: 安部拓矢
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2018-12-19
Filing date: 2019-11-11
Publication date: 2023-07-07
Anticipated expiration: 2039-11-11
Also published as: KR20210104702A; CN113194922A; EP3900700A1; JP7048480B2; WO2020129461A1; US20220062121A1; EP3900700A4; EP3900700B1; JP2020100565A

Abstract

The present invention provides a microemulsion composition comprising (A) an anionic surfactant, (B) an organopolysiloxane having at least two hydrosilyl groups in one molecule represented by the following formula (I), (C) an organopolysiloxane having at least two ethylenically unsaturated groups in one molecule represented by the following formula (II), (D) a monohydric or polyhydric alcohol, and (E) water, wherein the microemulsion composition has a transparent or translucent appearance at 25 ℃. Thus, when an organopolysiloxane having a reactive functional group such as a hydrosilyl group or an ethylenically unsaturated group is used in the oil phase, a microemulsion composition having a transparent or translucent appearance can be provided.

Description

Microemulsion composition, cured product thereof, and cosmetic containing cured product thereof

Technical Field

The present invention relates to a microemulsion composition, a cured product thereof, and a cosmetic containing the cured product.

Background

Transparent or semitransparent microemulsion composed of surfactant, water phase and oil phase is roughly divided into three kinds of water-dispersible emulsion with continuous phase of water, oil-dispersible emulsion with continuous phase of oil and bicontinuous emulsion with continuous phase composed of water and oil. In particular, cosmetic compositions having a bicontinuous structure which can improve the functionality and the feel of use include compositions used as a cleanser or a cleanser for skin and hair (patent documents 1 to 7).

In comparison with a water-dispersible emulsion or an oil-dispersible emulsion, a bicontinuous microemulsion composition requires the use of a large amount of a surfactant, but when used as a cosmetic, the surfactant may remain as a sticky or greasy feel, and thus the amount of the surfactant may be reduced in order to maintain a light touch (patent document 8). In addition, when silicone oil is used in the oil phase, although the touch feeling can be improved, few examples have been reported, and the types of surfactants have been limited.

By using a surfactant (Surfactin) as a natural surfactant, a silicone oil-containing microemulsion composition can be produced. Patent document 9 reports an emulsion composition comprising a surfactant, an amino-modified silicone, and an aqueous solvent. The surfactant is characterized in that the emulsifying power is high, and a small amount of surfactant is required, but the surfactant is anionic, so that the surfactant has a sticky feel caused by the fact that the surfactant is more strongly remained than the nonionic surfactant. Furthermore, there are limited silicones which can be used, and there are no reports of organopolysiloxanes having reactive functional groups such as hydrosilyl groups or ethylenically unsaturated groups.

On the other hand, as a method for reducing the sticky feeling, it is known to use silicone particles capable of imparting a use feeling such as a dry feeling or a smooth feeling and extensibility (patent documents 10 and 11). In particular, silicone fine particles obtained by coating silicone rubber spherical particles with polyorganosilsesquioxane have soft touch and excellent dispersibility, and are therefore incorporated into many cosmetics. However, the production methods of the present invention are all carried out by using a water-dispersible emulsion having a cloudy appearance, and no report is made on the use of a microemulsion having a transparent appearance.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2009-196909

Patent document 2: japanese patent laid-open No. 2015-105255

Patent document 3: japanese patent laid-open publication No. 2017-66085

Patent document 4: japanese patent laid-open No. 2004-217640

Patent document 5: japanese patent laid-open publication No. 2013-32348

Patent document 6: japanese patent laid-open No. 2014-224061

Patent document 7: japanese patent application laid-open No. 2010-222324

Patent document 8: japanese patent laid-open No. 2011-178769

Patent document 9: international publication No. 2018/008653

Patent document 10: japanese patent application laid-open No. 2010-132877

Patent document 11: japanese patent laid-open publication No. 2017-193702

Patent document 12: international publication No. 2015/022936

Disclosure of Invention

Technical problem to be solved by the invention

In view of the above, an object of the present invention is to provide a microemulsion composition which is transparent or translucent in appearance when an organopolysiloxane having a reactive functional group such as a hydrosilyl group or an ethylenically unsaturated group is used in an oil phase, a microemulsion addition-curable composition in a state where transparency is maintained, and a cosmetic containing the microemulsion addition-curable composition.

Technical means for solving the technical problems

In order to achieve the above object, the present invention provides a microemulsion composition characterized in that the microemulsion composition has a transparent or translucent appearance at 25 ℃ and is composed of:

(A) An anionic surfactant;

(B) An organopolysiloxane having at least two hydrosilyl groups in one molecule represented by the following formula (I),

[ chemical formula 1]

R ¹ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond; r is R ² Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond, and a part of the monovalent hydrocarbon groups may be hydrogen atoms; a is 0-300, b is 0-50, and 5-350, and when b=0, any two or more R's are used ² Is a hydrogen atom;

(C) An organopolysiloxane having at least two ethylenically unsaturated groups in one molecule represented by the following formula (II),

[ chemical formula 2]

R ³ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond; r is R ⁴ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having an aliphatic unsaturated bond having 2 to 30 carbon atoms or R ³ The method comprises the steps of carrying out a first treatment on the surface of the c is 0-500, d is 0-50, and 5-550, R when d=0 ⁴ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having an aliphatic unsaturated bond and having 2 to 30 carbon atoms;

(D) Monohydric or polyhydric alcohols;

(E) And (3) water.

In the case of the microemulsion composition of the present invention, the addition curing reaction can be carried out by adding a hydrosilylation catalyst without impairing the transparency of the appearance, and a transparent or translucent microemulsion addition curing composition can be produced.

In this case, the microemulsion composition is preferably dispersible when added to water.

Such a microemulsion composition can be suitably used for applications such as cosmetics.

Furthermore, it is preferable that the (a) anionic surfactant is a natural surfactant.

The anionic surfactant (a) can reduce the load on the environment, has high safety, and is suitable for use in a microemulsion composition.

In addition, it is preferable that the natural surfactant contains a cyclic peptide group represented by the following formula (III).

[ chemical formula 3]

Wherein X represents an amino acid residue selected from leucine, isoleucine and valine; r is R ⁵ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 9 to 18 carbon atoms and having no aliphatic unsaturated bond, L-Leu means L-leucine, D-Leu means D-leucine, L-Val means L-valine, and the counter ion (counter-ion) of the carboxyl group is composed of an alkali metal ion.

Thus, the natural surfactant is more preferably used in the microemulsion composition if it is a component represented by the formula (III).

In this case, X in the formula (III) is preferably leucine, R ⁵ Is a hydrocarbon chain having 12 carbon atoms.

If the natural surfactant represented by the above formula (III) is such a natural surfactant, it can be further suitably used in a microemulsion composition.

Furthermore, it is preferable that the content of the (A) anionic surfactant in the microemulsion composition is 0.1 to 10wt%.

When the content of the anionic surfactant (a) is such, a microemulsion can be sufficiently formed.

In addition, preferably, the (D) monohydric or polyhydric alcohol is glycerol.

If the monohydric or polyhydric alcohol (D) is glycerol, the D phase (surfactant phase) can be formed in a wide concentration range.

Furthermore, it is preferred that the microemulsion composition forms a bicontinuous structure.

Thus, when the microemulsion composition is formed into a bicontinuous structure, the functionality and the feel of use can be improved when a cosmetic is manufactured using the microemulsion composition.

Further, the hydrosilyl group contained in (B) is preferably 0.5 to 3.0 mol based on 1 mol of the ethylenically unsaturated group contained in (C).

If the hydrosilyl group is contained in the above (B) in such a molar amount, the addition curing reaction can be sufficiently performed in the addition curing of the microemulsion composition, and a sufficient touch feeling can be obtained. In addition, transparency after addition curing can be maintained.

Furthermore, it is preferred that the microemulsion composition is addition cured by addition of (F) a hydrosilylation catalyst.

Thus, the addition curing of the microemulsion composition described above is enabled by the addition of (F) a hydrosilylation catalyst.

The present invention also provides a microemulsion addition-curable composition comprising the microemulsion composition of the present invention, which is addition-cured and has a transparent or translucent appearance.

Such microemulsion addition cure compositions have an apparent clarity and can reduce the tackiness of anionic surfactants.

The present invention also provides a cosmetic composition comprising the above-described microemulsion addition curable composition.

Thus, the cosmetic containing the microemulsion addition curing composition can reduce the stickiness caused by the anionic surfactant, has good use feeling, refreshing feeling and stability with time, good makeup holding property, good extension or makeup feeling, and excellent rub-off resistance (rubfastness).

Effects of the invention

By adding a hydrosilylation catalyst, the microemulsion composition of the present invention can undergo an addition curing reaction without impairing the transparency of the appearance, and transparent or translucent microemulsion addition curing compositions can be produced. The cosmetic containing the microemulsion addition curing composition can reduce the stickiness caused by the anionic surfactant, has good use feeling, refreshing feeling and stability with time, good make-up holding property, good extension or make-up feeling and excellent rub resistance.

Detailed Description

The present invention will be described in detail below, but the present invention is not limited thereto.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that an organopolysiloxane having a reactive functional group such as a hydrosilyl group or an ethylenically unsaturated group represented by the following formulas (I) and (II) is used as an oil phase, and thus it is easy to provide a microemulsion composition having a transparent or translucent appearance. It has also been found that by adding a hydrosilylation catalyst to the microemulsion composition described above, a clear or translucent microemulsion addition cure composition can be produced. It has been found that a cosmetic containing the obtained microemulsion addition-curable composition can reduce the tackiness caused by an active agent, and can provide a cosmetic excellent in feeling in use, refreshing feeling and stability with time, and the present invention has been completed.

That is, the present invention is a microemulsion composition which contains the following (A) to (E) and has a transparent or translucent appearance at 25 ℃.

(A) An anionic surfactant;

[ chemical formula 4]

[ chemical formula 5]

(D) Monohydric or polyhydric alcohols;

(E) And (3) water.

In the case of such a microemulsion composition, addition curing reaction can be performed by adding a hydrosilylation catalyst without impairing the transparency of the appearance, and a transparent or translucent microemulsion addition curing composition can be produced.

[ component A ]

The anionic surfactant (a) used in the present invention has an anionic hydrophilic group in its molecular structure and is formed of a linear or branched hydrocarbon chain as a hydrophobic group, an aromatic ring or a heterocyclic ring, and a group formed by combining these groups. Examples thereof include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, condensate salts of amino acids and fatty acids, alkane sulfonates, olefin sulfonates, sulfonates of fatty acid esters, sulfonates of fatty acid amides, formalin condensate sulfonates, alkyl sulfate salts, higher secondary alcohol sulfate salts, alkyl and allyl ether sulfate salts, sulfate salts of fatty acid esters, sulfate salts of fatty acid alkanolamides, sulfate salts such as turkish oil, alkyl phosphates, ether phosphates, alkyl allyl ether phosphates, amide phosphates, N-acyl lactates, N-acyl sarcosinates, N-acyl amino acid activators, and natural surfactants typified by lecithin-bile acid surfactants. These anionic surfactants may be used alone or in combination of two or more. Particular preference is given to using natural surfactants.

The natural surfactant is a surfactant derived from a living body component, which is highly safe and is used for reducing the load on the environment. The synthetic surfactant is large in volume as compared with a general synthetic surfactant, has a chemical structure specific in terms of having a polyfunctional property, does not contain a petroleum-derived component, and therefore has been attracting attention in recent years because it has characteristics such as a special functionality, biodegradability, low toxicity, and bioactivity. Specifically, lecithin, bile acid, and surfactant are exemplified, and among these natural surfactants, use of surfactant is particularly preferable.

The surfactant is a natural surfactant containing a cyclic peptide group represented by the following formula (III). The surfactant is a biosurfactant (biosurfactant) produced by bacillus subtilis, and has a hydrophilic part of a cyclic peptide structure with 7 amino acids as constituent elements and a hydrophobic part composed of hydrocarbon groups. The surfactant is a generic term for compounds having different alkyl chain lengths or branched chain lengths of hydrocarbon groups. The sodium salt of surfactin is less skin irritating than other anionic surfactants. Furthermore, the cyclic peptide structures are attracted to each other between molecules through hydrogen bonds, thereby having a property of exhibiting a very low value of 0.0003wt% of critical micelle concentration.

[ chemical formula 6]

Wherein X represents an amino acid residue selected from leucine, isoleucine and valine, R ⁵ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 9 to 18 carbon atoms and having no aliphatic unsaturated bond, L-Leu means L-leucine, D-Leu means D-leucine, L-Val means L-valine, and carboxyl groupThe counter ion of the radical consists of an alkali metal ion.

X is an amino acid residue selected from leucine, isoleucine and valine. Leucine is preferred.

R ⁵ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 9 to 18 carbon atoms and not having an aliphatic unsaturated bond. For example, an alkyl group having 9 to 18 carbon atoms, an aryl group, or an aralkyl group. More specifically, examples thereof include a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. Particularly preferred are a nonyl group having 9 to 12 carbon atoms, decyl group, undecyl group and dodecyl group.

In the natural surfactant (surfactant) containing a cyclic peptide group represented by the above formula (III), the amino acid residue is preferably leucine or R ⁵ The counter ion for the carboxyl group is preferably sodium ion, which is a hydrocarbon chain having 12 carbon atoms and containing a branched chain. As an example, the substance described in patent document 12 can be used. Such a substance is not limited to the following examples, and "KANEKA surface" manufactured by KANEKA CORPORATION may be used, for example.

[ component B ]

The organopolysiloxane having at least two hydrosilyl groups in one molecule used in the present invention (B) is represented by the following formula (I).

[ chemical formula 7]

R ¹ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond; r is R ² Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond, and a part of the monovalent hydrocarbon groups may be hydrogen atoms; a is 0-300, b is 0-50, and 5-350, and when b=0, any two or more R's are used ² Is a hydrogen atom; when b=1, any one or more of R ² Is a hydrogen atom.

In the above formula (I), R ¹ Each independently is of the number of carbon atoms1 to 30, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, which is substituted or unsubstituted and does not have an aliphatic unsaturated bond. For example, an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, an amino group, or a carboxyl group. Among them, alkyl groups having 1 to 10 carbon atoms, aryl groups, aralkyl groups, fluoroalkyl groups, chloroalkyl groups, amino-substituted alkyl groups, and carboxyl-substituted alkyl groups are preferable. More specifically, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, trifluoropropyl, heptadecafluorodecyl, chloropropyl, chlorophenyl, and the like are exemplified. Particularly preferred are alkyl groups having 1 to 5 carbon atoms, phenyl groups and trifluoropropyl groups.

In the above formula (I), R ² Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, having no aliphatic unsaturated bond, or a hydrogen atom. Examples of the hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, and a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, an amino group, or a carboxyl group. Among them, alkyl groups having 1 to 10 carbon atoms, aryl groups, aralkyl groups, fluoroalkyl groups, chloroalkyl groups, amino-substituted alkyl groups, and carboxyl-substituted alkyl groups are preferable. More specifically, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, trifluoropropyl, heptadecafluorodecyl, chloropropyl, chlorophenyl, and the like are exemplified. Particularly preferred are an alkyl group having 1 to 5 carbon atoms, a phenyl group, a trifluoropropyl group and a hydrogen atom.

In the above formula (I), a is 0.ltoreq.a.ltoreq.300, preferably 10.ltoreq.a.ltoreq.100. If a is more than 300, the stability after emulsification becomes poor due to the larger molecular structure. b is 0.ltoreq.b.ltoreq.50, preferably 0.ltoreq.b.ltoreq.30. If b is greater than 50, the crosslinking points in the addition reaction become large, and the resulting cured product becomes hard and gives a touch to be impaired. a+b is 5.ltoreq.a+b.ltoreq.350, preferably 10.ltoreq.a+b.ltoreq.150. If a+b is less than 5, the molecular weight of the cured product after the addition reaction becomes small, and the properties of the obtained cured product are close to liquid, and the touch is impaired. If a+b is greater than 350, the molecular structure becomes large, and the stability after emulsification becomes poor.

[ component C ]

The organopolysiloxane having at least two ethylenically unsaturated groups in one molecule used in (C) of the present invention is represented by the following formula (II).

[ chemical formula 8]

R ³ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond; r is R ⁴ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having an aliphatic unsaturated bond having 2 to 30 carbon atoms or R ³ The method comprises the steps of carrying out a first treatment on the surface of the c is 0-500, d is 0-50, and 5-550, R when d=0 ⁴ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having an aliphatic unsaturated bond and having 2 to 30 carbon atoms.

In the above formula (II), R ³ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and having no aliphatic unsaturated bond. For example, an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, an amino group, or a carboxyl group. Among them, alkyl groups having 1 to 10 carbon atoms, aryl groups, aralkyl groups, fluoroalkyl groups, chloroalkyl groups, amino-substituted alkyl groups, and carboxyl-substituted alkyl groups are preferable. More specifically, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, phenyl, tolyl, trifluoropropyl, heptadecafluorodecyl, chloropropyl, chlorophenyl, and the like are exemplified. Particularly preferred are alkyl groups having 1 to 5 carbon atoms, phenyl groups and trifluoropropyl groups.

In the formula (II), R is ⁴ Each independently is a monovalent hydrocarbon group having 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms, substituted or unsubstituted with an aliphatic unsaturated bond, or R ³ The same groups. Examples of the hydrocarbon group having an aliphatic unsaturated bond include vinyl groups and alkene groupsPropyl, propenyl, hexenyl, styryl, and the like. Vinyl groups are particularly preferred. At R ⁴ And R is R ³ When the same is true, as described above.

In the formula (II), c is 0.ltoreq.c.ltoreq.500, and d is 0.ltoreq.d.ltoreq.50. c is 0.ltoreq.c.ltoreq.500, preferably 10.ltoreq.c.ltoreq.400. If c is more than 500, the molecular structure becomes large, and the stability after emulsification becomes poor. d is 0.ltoreq.d.ltoreq.50, preferably 0.ltoreq.d.ltoreq.30, and more preferably 0.ltoreq.d.ltoreq.10. If d is greater than 50, the crosslinking points in the addition reaction become large, and the resulting cured product becomes hard, and thus the touch is impaired. c+d is 5.ltoreq.c+d.ltoreq.550, preferably 10.ltoreq.c+d.ltoreq.400. If c+d is less than 5, the molecular weight of the cured product after the addition reaction becomes small, and the properties of the obtained cured product are close to liquid, and the touch is impaired. If c+d is greater than 550, the molecular structure becomes large, and the stability after emulsification becomes poor.

[ component D ]

As the monohydric or polyhydric alcohol (D) used in the present invention, there may be mentioned monohydric alcohols which are usually used, and concretely, polyhydric alcohols such as primary alcohols, lower alcohols or higher alcohols, erythritol, maltitol, xylitol, sorbitol and the like, and polyhydric alcohols such as 1,3-BG, glycerol, PG, DPG and the like, may be used singly or in combination. Particularly preferred is the use of water-soluble polyols.

As the polyhydric alcohol, one selected from the group consisting of a 1, 2-alkane diol having 5 to 10 carbon atoms and a polyhydric alcohol other than the same is preferably used, or two or more selected from the group consisting of a 1, 2-alkane diol having 5 to 10 carbon atoms and a polyhydric alcohol other than the same are used in combination. The use of the polyhydric alcohol can be combined with (a) an anionic surfactant to adjust HLB (Hydrophilic-lipophilic Balance), and thus phase D is easily formed.

Specifically, the 1, 2-alkane diol having 5 to 10 carbon atoms is 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, 1, 2-nonanediol, or 1, 2-decanediol. Among them, one or more of 1, 2-hexanediol, 1, 2-heptanediol and 1, 2-octanediol are preferably used.

The polyhydric alcohol other than the 1, 2-alkane diol having 5 to 10 carbon atoms is not particularly limited as long as it can be used as a cosmetic raw material, and examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerol, diglycerol, polyglycerol, 1, 3-butanediol, isopentyl glycol, sorbitol, mannitol, and glucitol (glycerin). Dipropylene glycol, glycerol, 1, 3-butanediol are particularly preferred. Further, when glycerol is used, the D phase can be formed in a wide concentration range, which is particularly preferable.

In the cosmetic, the total blending amount of the (D) monohydric alcohol or polyhydric alcohol is preferably set to 1.0 to 70% by mass, more preferably 5 to 50% by mass. When the amount is 1.0 mass% or more, a microemulsion can be sufficiently obtained.

[ method for producing microemulsion ]

The emulsification may be carried out using a usual emulsifying and dispersing machine, and examples thereof include a high-speed rotary centrifugal radial mixer such as a homogenizing and dispersing machine (homomixer), a high-speed rotary shear mixer such as a high-speed mixer, a high-pressure jet emulsifying and dispersing machine such as a homogenizer, a colloid mill, and an ultrasonic emulsifying machine.

When the five components (a) to (E) are mixed, a phase transition temperature emulsification method, a D-phase emulsification method, or the like (emulsification step) may be used.

The phase transition temperature emulsification method is a method of stirring around a phase transition temperature (PIT) commensurate with HLB, and then rapidly cooling to form a fine emulsion. In the vicinity of PIT, since the surface tension between oil and water is remarkably reduced, fine emulsion particles are easily generated.

The D-phase emulsification method adjusts the HLB of a surfactant by adding a water-soluble polyol, and after the D-phase is formed, a fine emulsion can be formed by adding oil, via an O/D emulsion, and by adding water.

In the case of the D-phase emulsification method, specifically, in a mixture of the (A) anionic surfactant and the polyol as the (D) component, the organopolysiloxane of the (B) component and the organopolysiloxane of the (C) component are slowly blended under the condition of shearing using a homogenizing dispenser, thereby forming the D-phase. Then, by slowly adding a prescribed amount of (E) water, a transparent or translucent microemulsion can be obtained.

The microemulsion has three types of micelle aqueous solution phase of oil-soluble in water, reverse micelle oil solution phase of water-soluble in oil and bicontinuous phase of water-oil continuous structure, and belongs to any phase.

Whether the microemulsion composition is aqueous or oily can be confirmed by the following method. The microemulsion composition is aqueous when it is rapidly and uniformly dispersed when it is added to a large excess of water and not dispersed when it is added to a large excess of oil, and conversely, it is oily when it is rapidly and uniformly dispersed when it is added to a large excess of oil and not dispersed when it is added to a large excess of water. The aqueous micelle solution in which oil is soluble in water is aqueous because it is rapidly dispersed when added to water and is not dispersed when added to oil. The water-soluble reverse micelle oil solution phase is oily because it does not disperse when added to water and rapidly disperses when added to oil. The bicontinuous phase of which the water and the oil are in continuous structures is any one of water-based or oil-based. The microemulsion compositions of the present invention preferably disperse when added to water. That is, it is preferable that the oil is soluble in water in either of a micelle aqueous solution and a bicontinuous phase in which water-oil is in a continuous structure.

Further, whether the microemulsion composition is in the micelle aqueous solution phase or in the bicontinuous phase can be confirmed by the following method.

The microemulsion compositions of the present invention preferably form a bicontinuous structure. The bicontinuous structure can be confirmed by electron microscopic observation based on the well-known freeze fracture replica method. Can be more easily confirmed by a pigment dispersion test. In the pigment dispersion test, the aqueous pigment and the oily pigment were added separately, and the mixture was rapidly mixed with both water and oil, thereby confirming the amphiphilicity.

The microemulsion composition of the present invention preferably contains 0.1 to 10wt% of (A) an anionic surfactant. The surfactant is excellent in emulsifying property, and thus an emulsion can be formed by adding a small amount.

In the microemulsion composition of the present invention, the content ratio of each of the components (B), (C), (D) and (E) is not particularly limited, and it is preferable that the content ratio of the organopolysiloxane of the component (B) is 10 to 500 parts by mass, the content ratio of the organopolysiloxane of the component (C) is 10 to 1000 parts by mass, the content ratio of the monohydric alcohol or polyhydric alcohol of the component (D) is 10 to 500 parts by mass, and the content ratio of the water of the component (E) is 10 to 800 parts by mass, based on 10 parts by mass of the anionic surfactant of the component (a).

[ method for producing microemulsion addition curable composition ]

The microemulsion composition of the present invention is preferably addition-cured by hydrosilylation reaction by adding (F) a hydrosilylation catalyst to the microemulsion composition described above. The hydrosilylation catalyst (F) may be added after the emulsification step of the microemulsion composition.

The hydrosilyl group contained in (B) is preferably 0.5 to 3.0 mol based on 1 mol of the ethylenically unsaturated group contained in (C). When the amount of the hydrosilane group is 0.5 mol or more, the subsequent addition curing reaction proceeds sufficiently, and a sufficient touch feeling can be obtained. In addition, when the amount of the hydrosilane group is 3.0 mol or less, the transparency of the microemulsion becomes good.

The hydrosilylation reaction is preferably carried out in the presence of a platinum group metal catalyst such as a platinum catalyst or a rhodium catalyst. The hydrosilylation catalyst (F) is preferably chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinyl siloxane complex, or the like. The amount of the catalyst to be used is preferably 50ppm or less, particularly preferably 20ppm or less, based on the total amount of the microemulsion composition, based on the amount of platinum or rhodium. The use of such a catalyst can suppress coloring of the sample due to excessive content, and the transparency is improved.

The metal-based catalyst listed above is hydrophobic, and therefore, when added directly to an oil-in-water (micelle aqueous solution phase) microemulsion composition, the curing reaction rate may be slow. Therefore, it is preferable to coat the catalyst with a dispersing agent such as a nonionic surfactant to increase the reaction rate. On the other hand, since the microemulsion having a bicontinuous structure is a continuous phase of water and oil at the same time, the above-listed coating with a nonionic surfactant is not required. Therefore, the reaction can be easily performed by adding only the metal-based catalyst.

The platinum group metal catalyst may be added after the emulsification step as described above, but may be dissolved together with the component (B) and the component (C) in advance. When the platinum group metal catalyst is added after the emulsification step, the catalyst may be dissolved in a solvent. When the dispersibility in water is poor, it is preferable to add the platinum group metal catalyst in a state of being dissolved in the nonionic surfactant. When the platinum group metal catalyst is dissolved together with the component (B) and the component (C) in advance, it is preferable to cool the catalyst at a low temperature of, for example, 5 ℃ or less so that the addition reaction does not occur until the emulsification step is completed.

The addition reaction may be carried out at ordinary temperature, for example, at 20 to 25 ℃. The stirring time for the reaction is not particularly limited, and is usually 1 to 24 hours. When the reaction is not completed, it may be performed under heating at less than 100 ℃. By performing the process in such a temperature range, structural disintegration of the emulsion can be more reliably suppressed.

Furthermore, the present invention provides a microemulsion addition cure composition that has a transparent or translucent appearance after addition cure. In the case of a microemulsion addition-curable composition obtained by addition-curing a microemulsion composition containing the above (B) and (C), the influence on the phase of the emulsion due to heat generation associated with the addition-curing reaction or shrinkage of the structure can be suppressed, and the transparency after the reaction becomes good.

[ physical Properties of microemulsion addition curing composition ]

By blending the microemulsion addition curing composition of the present invention as a touch improver in a cosmetic, the tackiness caused by a surfactant can be reduced, and a cosmetic excellent in feeling in use, refreshing feeling and stability with time can be obtained.

Furthermore, from the point of convenience of incorporation into aqueous or emulsion-type compositions, the present invention can produce a microemulsion addition-curable composition having a bicontinuous structure, which is used as an intermediate composition. That is, by adding water to the microemulsion addition curing composition of the present invention having a bicontinuous structure, a water-dispersible emulsion dispersed in an aqueous phase as an intermediate composition is first prepared, and then a cosmetic blended with the emulsion is produced.

[ cosmetics ]

The microemulsion addition curing composition of the present invention is useful for various purposes, and is particularly suitable as a raw material for all cosmetics for external application to the skin or hair. In this case, the blending amount of the microemulsion addition curing composition is preferably in the range of 0.1 to 40% by mass, more preferably in the range of 0.1 to 10% by mass, of the entire cosmetic. When the amount is 0.1 mass% or more, a sufficient touch feeling can be obtained, and when the amount is 40 mass% or less, the feeling of use is good.

[ other Components ]

The microemulsion addition curable composition of the present invention and the cosmetic containing the same may contain various components commonly used in cosmetics as other components. The other components may include, for example, an oil agent other than the components (B) and (C) as (G), a powder (H), a surfactant other than the component (a) as (I), a cross-linked organopolysiloxane (J), a film-forming agent (K), and other additives. These other components may be used singly or in combination of two or more. These components may be appropriately selected and used according to the type of cosmetic, etc., and the blending amount thereof may be a known blending amount corresponding to the type of cosmetic, etc.

(G) The method comprises the following steps Oil agent other than the components (B) and (C)

In the cosmetic of the present invention, one or two or more oils selected from the oils other than the components (B) and (C) as the component (G) may be blended depending on the purpose. Any of solid, semisolid, and liquid oils may be used as long as they are components used in cosmetics, and for example, natural animal and vegetable oils and fats, semisynthetic oils, hydrocarbon oils, higher alcohols, ester oils, commonly used silicone oils, fluorine-based oils, ultraviolet absorbers, and the like may be used. When blending the oil, the blending amount of the oil is not particularly limited, but is preferably 1 to 95% by mass, more preferably 1 to 30% by mass of the whole cosmetic.

Silicone oil

Examples of the silicone oil include low-viscosity to high-viscosity linear or branched organopolysiloxanes such as dimethylpolysiloxane, tris (trimethylsiloxy) methylsilane, octylpolymethylsiloxane, phenylpolytrimethylsiloxane, tetrakis (trimethylsiloxy) silane, methylphenylpolysiloxane, methylhexylpolysiloxane, polymethylhydrosiloxane, dimethylsiloxane-methylphenylsiloxane copolymer, cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrocyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, amino-modified organopolysiloxane, pyrrolidone-carboxylic acid-modified organopolysiloxane, high-polymerization-degree colloidal dimethylpolysiloxane, colloidal dimethylsiloxane-methylphenylsiloxane copolymer, and cyclic organopolysiloxane solutions of silicone rubber or rubber, higher alkoxy-modified silicones such as stearyloxy silicone, higher fatty acid-modified silicones, alkyl-modified silicones, long-chain alkyl-modified silicones, amino-acid-modified silicones, fluorine-modified silicones, and the like.

Natural animal and vegetable oils and fats and semisynthetic oils and fats

As natural animal and vegetable oils and fats and semisynthetic oils and fats, examples thereof include avocado oil, linseed oil, almond oil, white insect wax, perilla oil, olive oil, cocoa butter, kapok wax, torreya oil, carnauba wax, cod liver oil, candelilla wax, purified candelilla wax, tallow, beef foot fat, beef tallow, hydrogenated tallow, almond seed oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, camellia oil, safflower oil, shea butter, china tung oil, cinnamon oil, jojoba wax, squalane, squalene, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, japanese tung oil, rice bran wax, germ oil, horse fat apricot oil, palm kernel oil, castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape seed oil, bay wax, jojoba oil, macadamia nut oil, beeswax, mink oil, white pool seed oil, cotton wax, wood wax, japan wax oil, montan wax, coconut oil, hydrogenated coconut oil, coconut oil fatty acid triglycerides, lanolin, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, acetylated lanolin alcohol, isopropyl lanolin fatty acid, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol ester, POE hydrogenated lanolin alcohol ether, egg yolk oil, and the like. Wherein POE represents polyoxyethylene.

Hydrocarbon oil

Examples of the hydrocarbon oil include linear, branched and volatile hydrocarbon oils, and specifically include ceresin (ozokerite), α -olefin oligomers, light isoparaffins, isododecane, isohexadecane, light liquid isoparaffins, squalane, synthetic squalane, vegetable squalane, squalene, ceresin (ceresin), paraffin (paraffin), paraffin wax (paraffin wax), polyethylene wax, polyethylene-polypropylene wax, (ethylene/propylene/styrene) copolymers, (butene/propylene/styrene) copolymers, mobile paraffin, liquid isoparaffins, pristane, polyisobutylene, hydrogenated polyisobutene, microcrystalline wax, vaseline, higher fatty acids, and the like. Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

Higher alcohols

Examples of the higher alcohol include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, cetyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecyl alcohol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerol ether (batyl alcohol), and monooleyl glycerol ether (squalol).

Ester oil

As the ester oil, there is used, examples thereof include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyl dodecyl gum, oleyl oleate, octyl dodecyl oleate, decyl oleate, neopentyl glycol dioctate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesterol 12-hydroxystearate, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl laurate, isopropyl lauroyl sarcosinate, diisostearyl malate, glyceride and the like. Examples of the glyceride oil include acetylglyceride, triisocaprylin, triisostearin, triisopalmitin, tribenzylbehenate, glyceryl monostearate, di-2-heptylundecylenate, trimyristate, and diglycidylester.

Fluorine-based oil

As the fluorine-based oil agent, there is used, examples thereof include perfluoropolyethers, perfluorodecalins, perfluorooctanes, and the like.

Ultraviolet absorber

Examples of the ultraviolet absorber include benzoic acid ultraviolet absorbers such as p-aminobenzoic acid, anthranilic acid ultraviolet absorbers such as methyl anthranilate, salicylic acid ultraviolet absorbers such as methyl salicylate, octyl salicylate, and trimethylcyclohexyl salicylate, cinnamic acid ultraviolet absorbers such as octyl p-methoxycinnamate, benzophenone ultraviolet absorbers such as 2, 4-dihydroxybenzophenone, urocanic acid ultraviolet absorbers such as ethyl urocaniate, dibenzoylmethane ultraviolet absorbers such as 4-tert-butyl-4' -methoxy-dibenzoylmethane, phenylbenzimidazole sulfonic acid, and triazine derivatives. The ultraviolet light absorber may contain an ultraviolet light absorbing and scattering agent. Examples of the ultraviolet light absorbing and scattering agent include powders that absorb and scatter ultraviolet light, such as particulate titanium oxide, particulate iron-containing titanium oxide, particulate zinc oxide, particulate cerium oxide, and a composite thereof, and a dispersion in which these powders that absorb and scatter ultraviolet light are dispersed in an oil solution in advance may be used.

(H) Powder body

The powder may be any powder used for a general cosmetic, and may be used regardless of its shape (spherical, needle-like, plate-like, etc.), its particle diameter (aerosol, fine particles, pigment grade, etc.), and its particle structure (porous, nonporous, etc.). Examples thereof include silicone spherical powder, inorganic powder, organic powder, surfactant metal salt powder, colored pigment, pearlescent pigment, metal powder pigment, tar pigment, natural pigment, and the like.

Inorganic powder

Specifically, examples of the inorganic powder include powders selected from titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lepidolite, silicic acid anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, gibbsite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, calcium hydrogen phosphate, aluminum oxide, aluminum hydroxide, boron nitride, and silica.

Organic powder

Examples of the organic powder include powders selected from polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzomelamine powder, polymethylbenzomelamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, 12 nylon, 6 nylon, silicone powder, styrene-acrylic copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenol resin, fluorine resin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine, and the like.

Surfactant metal salt powder

Examples of the surfactant metal salt powder (metal soap) include powders selected from zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, zinc sodium cetyl phosphate, and the like.

Colored pigments

Examples of the colored pigment include powders such as inorganic red pigments selected from iron oxide, iron hydroxide, iron titanate, inorganic brown pigments such as γ -iron oxide, inorganic yellow pigments such as yellow iron oxide and loess, inorganic black pigments such as black iron oxide and carbon black, inorganic violet pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as deep blue and ultramarine, pigments obtained by lake a tar pigment, pigments obtained by lake a natural pigment, and synthetic resin powders obtained by compounding these powders.

Pearlescent pigment

Examples of the pearlescent pigment include powders selected from titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated colored mica, and the like.

Metal powder pigment

Examples of the metal powder pigment include powders selected from aluminum powder, copper powder, stainless steel powder, and the like.

Tar pigment

Examples of the tar pigment include powders selected from red No. 3, red No. 104, red No. 106, red No. 201, red No. 202, red No. 204, red No. 205, red No. 220, red No. 226, red No. 227, red No. 228, red No. 230, red No. 401, red No. 505, yellow No. 4, yellow No. 5, yellow No. 202, yellow No. 203, yellow No. 204, yellow No. 401, blue No. 1, blue No. 2, blue No. 201, blue No. 404, green No. 3, green No. 201, green No. 204, green No. 205, orange No. 201, orange No. 203, orange No. 204, orange No. 206, orange No. 207, and the like.

Natural pigment

Examples of the natural pigment include powders selected from carminic acid, shellac pigment, carthamin, brasilinin, and crocin.

These powders may be obtained by compounding the powders or may be processed with a general oil, silicone oil, fluorine compound, surfactant, or the like. One or two or more of the following may be used as needed: a component obtained by treating an alkyl group having a hydrolyzable silane group or a hydrogen atom directly bonded to a silicon atom, a linear and/or branched organopolysiloxane having a hydrolyzable silane group or a hydrogen atom directly bonded to a silicon atom and co-modified with a long alkyl group, a linear and/or branched organopolysiloxane having a hydrolyzable silane group or a hydrogen atom directly bonded to a silicon atom and co-modified with a polyoxyalkylene, an acrylic-silicone copolymer having a hydrolyzable silane group or a hydrogen atom directly bonded to a silicon atom, or the like. More preferred are silicone treatments, such as silanes or silylating agents such as octylsilane (Shin-Etsu Chemical Co., ltd.: AES-3083) or trimethoxysilylmethylpolydimethylsiloxanes, dimethylsilicones (Shin-Etsu Chemical Co., ltd.: KF-96A series), methyl hydrogen polysiloxanes (Shin-Etsu Chemical Co., ltd.: KF-99P, KF-9901, etc.), silicone branched silicone treatments (Shin-Etsu Chemical Co., ltd.: KF-9908, KF-9909, etc.), and silicone acrylates (Shin-Etsu Chemical Co., ltd.: KP-574, etc.), etc. Specific examples of the surface-treated coloring pigment include Shin-Etsu Chemical co., ltd: KTP-09 series include KTP-09W, 09R, 09Y, 09B, and the like. Specific examples of the dispersion containing the hydrophobized fine particulate titanium oxide or the hydrophobized fine particulate zinc oxide include Shin-Etsu Chemical co..ltd.: SPD-T5, T6, T7, T5L, Z5, Z6, Z5L, etc.

Organosilicon spherical powder

Examples of the silicone spherical powder include a crosslinked silicone powder (i.e., a so-called silicone rubber powder formed of organopolysiloxane having a structure in which repeating chains of diorganosiloxane units are crosslinked), silicone resin particles (polyorganosilsesquioxane resin particles having a three-dimensional network structure), and silicone resin-coated silicone rubber powder.

Specific examples of the crosslinked silicone powder and silicone resin particles include those known by the names of (dimeric methyl siloxane/vinyl dimeric methyl siloxane) crosslinked polymers and polymethylsilsesquioxanes. These components are commercially available as powders or as swellings containing silicone oils, for example, under the product names of KMP-598, 590, 591, KSG-016F, etc. (all manufactured by Shin-Etsu Chemical Co., ltd.). These powders impart smoothness to cosmetics due to the rolling effect peculiar to spherical powders, and improve the feeling of use. These powders may be used singly or in combination.

Silicone resin-coated silicone rubber powder is particularly preferred from the viewpoint of improving the touch feeling effect such as preventing stickiness and the like, and the effect of correcting irregularities such as wrinkles and pores and the like. As specific examples of the silicone resin-coated silicone rubber powder, a (vinyl-dimeric methyl siloxane/polymethylsiloxane silsesquioxane) crosslinked polymer, (diphenyl-dimeric methyl siloxane/vinyl-diphenyl-dimeric methyl siloxane/silsesquioxane) crosslinked polymer, a polyorganosiloxane-22 (polysilicone-22), a polyorganosiloxane-1 crosslinked polymer, or the like, which is defined by the following cosmetic display names, may be used. These are commercially available under the product names of KSP-100, 101, 102, 105, 300, 411, 441, etc. (all Shin-Etsu Chemical Co., ltd.). These powders may be used singly or in combination.

When the powder is blended, the blending amount of the powder is not particularly limited, but is preferably 0.1 to 90% by mass, more preferably 1 to 35% by mass of the whole blended cosmetic.

(I) Surfactants other than component (A)

The surfactant other than the component (a) is not particularly limited, and any of nonionic, cationic and amphoteric surfactants may be used as long as they are surfactants commonly used in cosmetics, and one or two or more surfactants may be used alone or in combination as appropriate.

Among these surfactants, from the point of compatibility with the oil containing the component (a), crosslinked polyether-modified silicone, crosslinked polyglycerol-modified silicone, linear or branched polyoxyethylene-modified organopolysiloxane, linear or branched polyoxyethylene polyoxypropylene-modified organopolysiloxane, linear or branched polyoxyethylene-alkyl co-modified organopolysiloxane, linear or branched polyoxyethylene polyoxypropylene-alkyl co-modified organopolysiloxane, linear or branched polyglycerol-alkyl co-modified organopolysiloxane are preferable.

Among these surfactants, the content of hydrophilic polyoxyethylene groups, polyoxyethylene polyoxypropylene groups or polyglycerol residues is preferably 10 to 70% of the molecule. Specific examples of such surfactants include Shin-Etsu Chemical co., ltd. KSG-210, 240, 310, 320, 330, 340, 320Z, 350Z, 710, 810, 820, 830, 840, 820Z, 850Z, KF-6011, 6013, 6017, 6043, 6028, 6038, 6048, 6100, 6104, 6105, 6106, and the like.

When component (I) is blended, the blending amount is preferably 0.01 to 15% by mass in the cosmetic.

(J) Crosslinked organopolysiloxane

The cross-linking organopolysiloxane is not particularly limited as long as it is a cross-linking organopolysiloxane that is generally used in cosmetics, and two or more kinds may be used singly or in combination as appropriate.

The crosslinked organopolysiloxane has no spherical shape unlike the silicone spherical powder described in (H) above.

The component (J) is preferably a compound having no polyether or polyglycerol structure in the molecular structure, unlike the surfactant (I) other than the component (A). Further, it is an elastomer having structural viscosity by swelling with an oil agent. As specific examples, there may be mentioned (dimeric methyl siloxane/vinyl dimeric methyl siloxane) crosslinked polymer, (dimeric methyl siloxane/phenyl vinyl dimeric methyl siloxane) crosslinked polymer, (vinyl dimeric methyl siloxane/lauryl dimeric methyl siloxane) crosslinked polymer, (lauryl polydimethyl siloxane ethyl dimeric methyl siloxane/divinyl dimeric methyl siloxane) crosslinked polymer, and the like, which are defined by the cosmetic display names. Specific examples of such swellings containing oil, which are liquid at room temperature, are commercially available, and KSG-15, 1510, 16, 1610, 18A, 19, 41A, 42A, 43, 44, 042Z, 045Z, 048Z and the like manufactured by Shin-Etsu Chemical Co.Ltd.

The blending amount of the component (J) is preferably 0.01 to 30% by mass in terms of solid content in the cosmetic.

(K) Film coating agent

As the film forming agent, a conventional film forming agent can be used at the same time. The conventional film-coating agent is not particularly limited as long as it is a raw material that can be blended into cosmetics in general, and specifically, latex-based materials such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and polyalkyl acrylate can be used; cellulose derivatives such as dextrin, alkyl cellulose or nitrocellulose; organosilicon resins such as organosilicon-silicone graft copolymers, e.g., organosilicon polysaccharide compounds such as pullulan (tri (trimethylsilyl) silylpropyl carbamate), and (alkyl acrylate/dimeric methyl siloxane) copolymers; silicone resins such as silicone-modified polynorbornene and fluorine-modified silicone resins; fluorine resins, aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutenes, polyisoprenes, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, polyurethanes, and the like.

Among them, a silicone-based film coating agent is particularly preferable, and among them, pullulan tris (trimethylsiloxy) silylcarbamate (commercially available as a solvent-dissolved product, shin-Etsu Chemical co., ltd. Manufactured: TSPL-30-D5, ID), (alkyl acrylate/dimeric methylsiloxane) copolymer (commercially available as a solvent-dissolved product, shin-Etsu Chemical co., ltd. Manufactured: KP-543, 545, 549, 550, 545L, etc.), trimethylsiloxy silicic acid (commercially available as a solvent-dissolved product, shin-Etsu Chemical co., ltd. Manufactured: KF-7312J, X-21-5250, etc.), silicone-modified polynorbornene (commercially available as a solvent-dissolved product, shin-Etsu Chemical co., ltd. Manufactured: NBN-30-ID, etc.), and silicone grafted polyvinyl alcohol polymer, etc. can be used, but are not limited thereto.

The blending amount in blending the component (K) is preferably 0.1 to 20% by mass in the cosmetic.

(L) other additives

Examples of the other additives include oil-soluble gels, water-soluble tackifiers, antiperspirants, antiseptic/antiseptic agents, perfumes, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, components for skin beauty (whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, clathrate compounds, etc. These (L) components may be used singly or in combination of two or more. The blending amount of the component (L) is preferably 0.1 to 20% by mass in the cosmetic.

Oil-soluble gel

Examples of the oil-soluble gelling agent include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid, alpha, gamma-di-N-butylamine, etc.; dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; fructo-oligosaccharide fatty acid esters such as fructo-oligosaccharide stearate and fructo-oligosaccharide 2-ethylhexanoate; shan Benya benzylidene derivatives of sorbitol such as methyl sorbitol and benzhydrylidene sorbitol; and organically modified clay minerals of disteardimonium hectorite, sela ammonium hectorite, and the like.

Water-soluble adhesion promoter

As the water-soluble tackifier, a water-soluble tackifier, examples thereof include gum arabic, tragacanth, galactan, carob bean gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (marmelo), starch (rice, corn, potato, wheat, etc.), seaweed gum (algae gel), welt gum (tran gum), locust bean gum, etc., xanthan gum, dextran, succinoglycan, pullulan, etc., collagen, casein, albumin, gelatin, etc., carboxymethyl starch, methyl hydroxypropyl starch, etc., starch, methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, etc cellulose polymers such as sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cationized cellulose, and cellulose powder, alginic acid polymers such as sodium alginate and propylene glycol alginate, vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymers, polyoxyethylene polyoxypropylene copolymer polymers, acrylic polymers such as sodium polyacrylate, ethyl polyacrylate, polyacrylamide, and acryl dimethyl taurate copolymer, other synthetic water-soluble polymers such as polyethyleneimine and cationic polymer, bentonite, aluminum magnesium silicate, montmorillonite, bedstone, nontronite, soapstone, hectorite, and inorganic water-soluble polymers such as anhydrous silicic acid.

Among them, a water-soluble thickener is preferably used which is one or a combination of two or more selected from the group consisting of a plant-based polymer, a microorganism-based polymer, an animal-based polymer, a starch-based polymer, a cellulose-based polymer, an alginic acid-based polymer, a polyoxyethylene polyoxypropylene copolymer-based polymer, an acrylic acid-based polymer and an inorganic water-soluble polymer.

Antiperspirant

Examples of the antiperspirant include aluminum hydroxyhalides such as aluminum chloroxide and aluminum chloroxide, aluminum halides such as aluminum chloride, aluminum allantoin salts, tannins, persimmon tannins, aluminum potassium sulfate, zinc oxide, zinc sulfanilate, alum, tetrachloro (Al/zirconium) hydrate, and trichloro-hydrated glycine (Al/zirconium). As the component exhibiting high effect, aluminum hydroxyhalides, aluminum halides, and complexes or mixtures thereof with zirconyl oxyhalides and zirconyl hydroxyhalides (for example, tetrachloro (Al/zirconium) water and compounds, trichloro-hydrated glycine (Al/zirconium)) and the like are particularly preferable.

Sterilizing preservative

Examples of the antiseptic include alkyl p-hydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropyl methylphenol, phenol, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, triclosan, iodopropynyl butylcarbamate, polylysine, photoreceptors, silver, and plant extracts.

Perfume(s)

As the perfume, there are natural perfumes and synthetic perfumes. Natural flavors include plant flavors isolated from flowers, leaves, wood, pericarps, and animal flavors such as musk and musk. Examples of the synthetic perfume include hydrocarbons such as monoterpenes, alcohols such as aliphatic alcohols and aromatic alcohols, aldehydes such as terpene aldehydes and aromatic aldehydes, ketones such as alicyclic ketones, esters such as terpene esters, lactones, phenols, oxides, nitrogen-containing compounds, acetals, and the like.

Salts of

Examples of the salts include inorganic salts, organic acid salts, amine salts and amino acid salts. Examples of the inorganic salts include sodium, potassium, magnesium, calcium, aluminum, zirconium, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid. Examples of the organic acid salt include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid. Examples of the amine salts and amino acid salts include salts of amines such as triethanolamine and salts of amino acids such as glutamic acid. In addition, salts of hyaluronic acid, chondroitin sulfate and the like, or further, acid-base neutralization salts used in the formulation, and the like can be used in addition to the above salts.

Antioxidant(s)

Examples of the antioxidant include, but are not particularly limited to, carotenoids, ascorbic acid and salts thereof, ascorbyl stearate, tocopherol, tocopheryl acetate, tocopherol, p-tert-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfite, isoascorbic acid and salts thereof, chlorogenic acid, epicatechin, epigallocatechin gallate, apigenin, kaempferol, myricetin, quercetin, and the like.

pH regulator

Examples of the pH regulator include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogencarbonate, and ammonium hydrogencarbonate.

Chelating agent

Examples of the chelating agent include alanine, edetic acid sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like.

Cooling agent

Examples of the cooling agent include L-menthol, camphor, menthyl lactate, and the like.

Antiphlogistic agent

Examples of the anti-inflammatory agent include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid stearate, tranexamic acid, azulene, and the like.

Component for beautifying skin

Examples of the component for beauty include whitening agents such as placenta extract, arbutin, glutathione and saxifraga stolonifera extract, cell activators such as royal jelly, photoreceptor, cholesterol derivatives and calf blood extract, skin roughness improvers, vanillylamide nonanoate, benzyl nicotinate, β -butoxyethyl nicotinate, capsaicin, zingibone, cantharidin, ichthyol, caffeine, tannic acid, α -borneol, tocopherol nicotinate, inositol nicotinate, cyclic mandelate, cinnarizine, tolassine, blood circulation accelerators such as acetylcholine, verapamil, cepharanthine and γ -oryzanol, and anti-seborrheic agents such as skin astringents, sulfur and dimethylthianthrene.

Vitamins

Examples of vitamins include vitamin A such as vitamin A oil, retinol acetate, retinol palmitate, and vitamin B such as riboflavin, riboflavin butyrate, and flavin adenine dinucleotide ₂ Vitamin B such as pyridoxine hydrochloride, pyridoxine dioctate, pyridoxine tripalmitate and the like ₆ Retinoids, vitamin B ₁₂ And derivatives, vitamin B thereof ₁₅ And derivatives thereof, vitamin B, vitamin C, such as L-ascorbic acid, L-ascorbyl dipalmitate, L-ascorbic acid-2-sodium sulfate, and L-ascorbyl dipotassium phosphate, vitamin D, such as ergocalciferol and cholecalciferol, vitamin E, such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, dl-alpha-tocopherol acetate, dl-alpha-tocopherol nicotinate, and dl-alpha-tocopherol succinate, niacin, nicotinic acid benzyl nicotinate, niacinamide, vitamin H, vitamin P, calcium pantothenate, D-panthenol, panthenol diethyl ether, panthenoate, and acetyl panthenoate diethyl ether.

Amino acids

Examples of the amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan and the like.

Nucleic acid

Examples of the nucleic acid include a deoxyribonucleic acid.

Hormone(s)

Examples of the hormone include estradiol and ethinyl estradiol.

Clathrate compound

The inclusion compound may be cyclodextrin or the like.

The cosmetic of the present invention is not particularly limited, and can be applied to various products such as a cosmetic liquid, an emulsion, a cream, a hair care agent (hair care), a foundation (foundation), a barrier cream, a sun block, a concealer, a blush, a lipstick, a lip gloss (gloss), a lipstick (balm), a mascara, an eye shadow, an eyeliner, a body cosmetic, a deodorant, and a nail cosmetic. Among them, makeup cosmetics such as foundations, lipsticks, mascaras, eyeliners, and the like, or cosmetics having a sunscreen effect are particularly preferable.

The cosmetic of the present invention may be in the form of liquid, paste, solid, paste, gel, silk, schulped, clay, powder, stick, etc.

Examples

The present invention will be described more specifically below by way of examples and comparative examples of the present invention, but the present invention is not limited to the examples described below.

Examples 1 to 11

SFNa (KANEKA surfactant, KANEKA CORPORATION) as an anionic surfactant, organopolysiloxanes (1) to (3) as organopolysiloxane having at least two hydrosilyl groups in one molecule, organopolysiloxanes (4) to (6) as organopolysiloxane having at least two ethylenically unsaturated groups in one molecule, glycerol as a polyol of one of (D) monohydric or polyhydric alcohols, decamethylcyclopentasiloxane (KF-995) or linear organopolysiloxane (KF-96A-6 cs) as an oil other than (B) and (C) components were added to 200mL glass beakers, respectively (viscosity at 25 ℃ is 20mm ² Silicone oil containing no hydrosilyl group or ethylenic unsaturated group and not more than/s), isododecane as volatile hydrocarbon oil, and 2-ethylhexyl palmitate as ester oil, and then stirring and dissolving the mixture at room temperature using a disperser, and then adding (E) water dropwise at room temperature to prepare a microemulsion. In tables 2 to 3, the blending amount is expressed as mass%. In addition, the kinematic viscosity, vinyl content and hydrosilane content of the organopolysiloxanes (1) to (6) are shown in table 1.

[ chemical formula 9]

< organopolysiloxane (1) >

< organopolysiloxane (2) >

< organopolysiloxane (3) >

< organopolysiloxane (4) >

< organopolysiloxane (5) >)

< organopolysiloxane (6) >

TABLE 1

For water dispersibility, 1 drop of the microemulsion prepared in examples 1 to 11 was added to 10ml of water, and the dispersibility was examined (water dispersibility test). Similarly, for oil dispersibility, 1 drop of microemulsion was added to 10ml of D5 (decamethyl cyclopentasiloxane) solution, and the dispersibility was examined (oil dispersibility test). The results are shown in tables 2 to 3 together with the evaluation of the appearance of the microemulsion at 25 ℃.

TABLE 2

TABLE 3

As shown in tables 2 to 3, in examples 1 to 11, microemulsions having a transparent or semitransparent appearance at 25℃were obtained. The microemulsions were uniformly dispersed in water after being added dropwise, and therefore dispersibility in water was confirmed. On the other hand, the microemulsion was not dispersed in the oil after the dripping of the microemulsion into the oil, and separation occurred.

The colorless transparent or translucent microemulsions (examples 3 to 4, 6, 8 to 10) obtained were subjected to pigment dissolution test. As a test method, the solubility of the water-soluble pigment was examined by adding an aqueous solution (concentration 0.1 mass%) of a water-soluble pigment (blue No.) to the obtained microemulsion. In addition, for oil solubility, a decamethylcyclopentasiloxane solution (concentration 1.0 mass%) of an oil-soluble pigment (β carotene) was added to the obtained microemulsion in the same manner as described above, and the solubility was examined. The microemulsion was confirmed to have a bicontinuous structure by uniformly dissolving all of the water-soluble coloring matter and the oil-soluble coloring matter. The results are shown in Table 4.

TABLE 4

Examples 12 to 17

A200 mL glass beaker containing 100g of the microemulsion of examples 3 to 4, 6 and 8 to 10, which had a transparent or translucent appearance, was kept at 20 to 25℃on a stirring device, and while stirring in this state, 0.1g (5 ppm based on the total amount of the microemulsion composition) of a toluene solution of chloroplatinic acid-vinyl siloxane complex (platinum concentration; 0.5% by weight) was added thereto, and the mixture was stirred at the same temperature range as described above for 12 hours, whereby the addition curing reaction of the organopolysiloxane having a hydrosilyl group of (B) and the organopolysiloxane having a vinyl group of (C) was carried out to prepare a microemulsion addition curing composition. The progress of the reaction was confirmed by the disappearance of the peak-to-peak from the vinyl group as determined by NMR. The results of evaluation of the appearance of the microemulsion before the reaction and the addition cured product thereof at 25℃and the pigment solubility test, the water dispersibility test and the oil dispersibility test performed in the same manner as in examples 3 to 4, 6 and 8 to 10 are shown in Table 5.

TABLE 5

As shown in Table 5 above, in examples 12 to 17, microemulsion addition-curable compositions having a transparent or translucent appearance at 25℃were obtained. Thus, since the appearance before the reaction was maintained, it was presumed that the effect of the curing reaction on the phase transfer was small. In addition, in the pigment solubility test, since all of the water-soluble pigment and the oil-soluble pigment were uniformly dissolved, it was confirmed that the microemulsion addition-curable composition after the reaction had a bicontinuous structure similar to that before the reaction. Further, after the microemulsion was added dropwise to water, the dispersibility in water was confirmed because all of the microemulsion was uniformly dispersed. On the other hand, after the microemulsion was added dropwise to the oil, the microemulsion was not dispersed in the oil, and separation occurred.

5g of the pre-reaction microemulsion and 5g of the post-reaction microemulsion addition-curable composition were each dispersed in 95ml of water to prepare aqueous dispersions thereof. About 0.02g of the prepared aqueous dispersion before and after the reaction was dropped onto the back of the hand using a dropper, and the mixture was spread with a finger to a size of about 2cm in diameter. After air-drying for 3 minutes, the microemulsion before the reaction had a sticky feeling due to the surfactant when strongly rubbed off with a finger, and the microemulsion after the reaction was rubbed into a solid component to be peeled off, thus suggesting the progress of the curing reaction. In addition, it was confirmed that the viscosity was reduced due to the influence of the solid content.

From this, it was confirmed that the addition-curable composition of the present invention can be subjected to an addition-curing reaction without impairing the transparency of the appearance by adding a hydrosilylation catalyst, and a transparent or translucent microemulsion addition-curable composition can be produced. In addition, it was confirmed that the microemulsion addition curing composition of the present invention had transparency in appearance, and reduced the tackiness by the anionic surfactant.

Comparative examples 1 to 4

SFNa (KANEKA surfactant, KANEKA CORPORATION) as an anionic surfactant, glycerol as a polyol of (D) a monohydric alcohol or a polyol, decamethylcyclopentasiloxane (KF-995) as a silicone oil containing no hydrosilyl group and an ethylenically unsaturated group, linear organopolysiloxane (KF-96A-6 cs), organopolysiloxane (7) represented by the following formula, and organopolysiloxane (8) represented by the following formula were each added to a glass beaker in the composition shown in Table 6, and the mixture was stirred and dissolved at room temperature using a disperser, and then (E) water was added dropwise at room temperature to prepare a microemulsion. The blending amount is expressed as mass%. The results of evaluation of the appearance of the microemulsion at 25 ℃, the pigment solubility test, the water dispersibility test, and the oil dispersibility test, which were performed in the same manner as in examples 3 to 4, 6, and 8 to 10, are shown in table 6.

[ chemical formula 10]

< organopolysiloxane (7) >

< organopolysiloxane (8) >

TABLE 6

As shown in table 6, clear-looking microemulsions were obtained in comparative examples 1 to 4. In the pigment solubility test, it was confirmed that the obtained microemulsion had a bicontinuous structure by uniformly dissolving all of the water-soluble pigment and the oil-soluble pigment. Further, all of the microemulsion was uniformly dispersed after being added dropwise to water, whereby dispersibility in water was confirmed.

About 0.02g of the aqueous dispersions of comparative examples 1 to 4 prepared in the same manner as in examples 12 to 17 were dropped onto the back of the hand using a dropper, and spread with the fingers to a size of about 2cm in diameter. After air-drying for 3 minutes, the product was rubbed off with a finger with a strong force, and had a tackiness due to the surfactant.

Example 18, comparative example 5

[ evaluation of Property ]

Based on the evaluation criteria shown in table 7, the cosmetics (examples 18 and 5) prepared using the microemulsion addition curable composition of example 12 and the microemulsion of comparative example 3 were applied to the skin, and the feel of use (no stickiness), the feel of freshness (tender feel) and the stability of the produced cosmetics with time (state after 1 month from 50 ℃ to 1 month storage) were evaluated. Based on the average of the professional participants (10), the result is determined according to the following determination criteria. The results are also shown in Table 8. Examples 18 and comparative example 5 were produced according to the formulations shown in table 8.

< production of cosmetics >

By uniformly mixing component (2) with component (1) in table 8, water-dispersible lotions (cosmetics of example 18 and comparative example 5) were obtained.

TABLE 7

Evaluating a certain criterion

Project	Feel in use	Refreshing feeling	Stability over time
				5 minutes	Good quality	Good quality	Good quality
4 minutes	Slightly better	Slightly better	Slightly better
				3 minutes	General	General	General
2 minutes	Slightly worse	Slightly worse	Slightly worse
				1 minute	Difference of difference	Difference of difference	Difference of difference

Determination criterion

And (3) the following materials: average division into more than 4.5 minutes

O: the average division is more than 3.5 and less than 4.5

Delta: the average division is more than 2.5 and less than 3.5

X: the average division is more than 1.5 and less than 2.5

X×: average score is less than 1.5 minutes

TABLE 8

From the results shown in Table 8, it is clear that the cosmetic (water-dispersible astringent) of the present invention has excellent feeling in use (no stickiness), refreshing feeling (water tenderness) and stability with time (state of 50 ℃ C. To 1 month).

In addition, the cosmetic of the present invention has good makeup retention, good extensibility and makeup feel, and excellent rub-off resistance.

The present invention is not limited to the above embodiments. The above embodiments are examples, and all embodiments having substantially the same constitution and exerting the same effects as the technical idea described in the claims of the present invention are included in the technical scope of the present invention.

Claims

1. A microemulsion composition characterized in that the microemulsion composition is transparent or translucent in appearance at 25 ℃ and consists of:

(A) An anionic surfactant;

R ¹ each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond; r is R ² Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and not having an aliphatic unsaturated bond, and a part of the monovalent hydrocarbon groups are optionally hydrogen atoms; a is 0-300, b is 0-50, and 5-350, and when b=0, any two or more R's are used ² Is a hydrogen atom;

(D) A polyol;

(E) Water;

the anionic surfactant (A) is a natural surfactant containing a cyclic peptide group represented by the following formula (III),

wherein X represents an amino acid residue selected from leucine, isoleucine and valine, R ⁵ Each independently is a substituted or unsubstituted monovalent hydrocarbon group having 9 to 18 carbon atoms and having no aliphatic unsaturated bond, L-Leu means L-leucine, D-Leu means D-leucine, and L-Val means L-valine; and the counter ion of the carboxyl group is composed of alkali metal ions.

2. The microemulsion composition of claim 1, wherein the microemulsion composition is dispersible when added to water.

3. The microemulsion composition of claim 1 wherein X in formula (III) is leucine, R ⁵ Is a hydrocarbon chain having 12 carbon atoms.

4. A microemulsion composition according to any one of claims 1 to 3 wherein the content of said (a) anionic surfactant in said microemulsion composition is from 0.1 to 10wt%.

5. A microemulsion composition according to any one of claims 1 to 3 wherein said (D) polyol is glycerol.

6. A microemulsion composition according to any one of claims 1 to 3 wherein the microemulsion composition forms a bicontinuous structure.

7. A microemulsion composition according to any one of claims 1 to 3 wherein said hydrosilane group contained in (B) is 0.5 to 3.0 mol relative to 1 mol of said ethylenically unsaturated group contained in (C).

8. A microemulsion composition according to any one of claims 1 to 3 wherein said microemulsion composition is addition cured by addition of (F) a hydrosilylation catalyst.

9. A microemulsion addition-curable composition, which is obtained by addition-curing the microemulsion composition according to claim 8, and which has a transparent or translucent appearance.

10. A cosmetic comprising the microemulsion addition curable composition of claim 9.